桥连[OSSO]型铪催化4-甲基-1-戊烯等规聚合研究

杨佳豪; 冯春玉; 周浩添; 涂广水; 郑涵斗; 高海洋

doi:10.11777/j.issn1000-3304.2025.25072

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桥连[OSSO]型铪催化4-甲基-1-戊烯等规聚合研究

研究论文 | 更新时间：2025-06-13

- 桥连[OSSO]型铪催化4-甲基-1-戊烯等规聚合研究
- Isotactic Polymerization of 4-Methyl-1-pentene Catalyzed by Bridged [OSSO]-Type Hafnium Complexes
- 高分子学报 2025年页码：1-9
- 作者机构：
  
  中山大学材料科学与工程学院聚合物复合材料及功能材料教育部重点实验室广州 510006
- 作者简介：
  
  E-mail: gaohy@mail.sysu.edu.cn
- 基金信息：
  
  国家重点研发计划(2021YFB3800701)
- DOI：10.11777/j.issn1000-3304.2025.25072
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7413
- 收稿日期：2025-03-14，
  
  录用日期：2025-05-08，
  
  网络出版日期：2025-06-12，
- 稿件说明：
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杨佳豪, 冯春玉, 周浩添, 涂广水, 郑涵斗, 高海洋. 桥连[OSSO]型铪催化4-甲基-1-戊烯等规聚合研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25072

Yang, J. H.; Feng, C. Y.; Zhou, H. T.; Tu, G. S.; Zheng, H. D.; Gao, H. Y. Isotactic polymerization of 4-methyl-1-pentene catalyzed by bridged [OSSO]-type hafnium complexes. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25072
杨佳豪, 冯春玉, 周浩添, 涂广水, 郑涵斗, 高海洋. 桥连[OSSO]型铪催化4-甲基-1-戊烯等规聚合研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25072 DOI： CSTR： 32057.14.GFZXB.2025.7413.

Yang, J. H.; Feng, C. Y.; Zhou, H. T.; Tu, G. S.; Zheng, H. D.; Gao, H. Y. Isotactic polymerization of 4-methyl-1-pentene catalyzed by bridged [OSSO]-type hafnium complexes. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25072 DOI： CSTR： 32057.14.GFZXB.2025.7413.

摘要

合成并表征了3种桥连[OSSO

]

型铪配合物Hf-Bn、Hf-Me和Hf-Cl，并系统研究了其对4M1P等规聚合的催化作用. Hf-Bn和Hf-Me在[Ph

]

[B(C

)

]

活化下，展现出了较高的催化活性(1.40×10

g PMP·(mol Hf)

-1

·h

-1

)；而Hf-Cl则需要MAO (methylaluminoxane)活化，其催化活性才能达到1.35×10

g PMP·(mol Hf)

-1

·h

-1

. 3种催化剂均展现出极高立构等规选择性(

98%). 所制备的聚(4-甲基-1-戊烯)具有高度等规立构性和高熔点，但重均分子量相对较低(

≈1×10

g·mol

-1

). 更深入的研究证实低分子量主要是聚合物增长链快速地向烷基铝链转移的结果.

Abstract

A series of bridged [OSSO

]

‍-type hafnium complexes (Hf-Bn

Hf-Me

and Hf-Cl) with different ancillary ligands were synthesized and characterized. After activation with [Ph

]

[B(C

)

]

or methylaluminoxane (MAO)

three bridged [OSSO

]

-type hafnium complexes showed good catalytic activity for 4-methyl-1-pentene (4M1P) polymerization. When the boron compound [Ph

]

[B(C

)

]

was used as an activator

alkyl hafnium complexes Hf-Bn and Hf-Me showed excellent catalytic activity of 1.40×10

g PMP·(mol Hf)

-1

·h

-1

. However

the chloride hafnium complex Hf-Cl achieved comparable activity (1.35×10

g PMP·(mol Hf)

-1

·h

-1

) only when methylaluminoxane (MAO) was used instead of [Ph

]

[B(C

)

]

. The three catalytic systems exhibited very high stereochemical selectivity. In comparison

Hf-Bn and Hf-Me systems afforded poly(4-methyl-1-pentene) (PMP) with higher isotacticity ([mmmm

]

98%) than Hf-Cl ([mmmm

]

= 92%). Hf-Bn was chosen to further study influences of 4M1P/Hf mole ratio

temperature and Al(TIBA)/Hf ratio on 4M1P polymerization. The catalytic activity and PMP molecular weight increased with increasing 4M1P/Hf molar ratio. Hf-Bn reached its maximum activity at 50 ℃. The molecular weight of PMP gradually decreased with increasing Al(TIBA)/Hf ratio

strongly indicating that chain transfer to Al occurred. The PMP samples were fully characterized by gel permeation chromatography (GPC)

H and

C-NMR

differential scanning calorimetry (DSC)

and wide-angle X-ray diffraction (WAXD). GPC analysis showed that the weight-average molecular weight of the produced PMPs was ~10000 g·mol

-1

H-NMR analysis further proved that the obtained PMP was fully saturated

which strongly supports the hypothesis that the low molecular weight of PMP is a result of the rapid occurrence of

chain transfer to aluminum. The obtained PMPs were highly isotactic (

98%) according to

C-NMR spectroscopy and had obvious melting temperatures (205-209 ℃) based on the DSC curves. WAXD analysis confirmed the crystalline architecture of the PMPs. The strain-stress curve of PMP shows brittle fracture characteristics

indicating that PMP is a brittle material with a fracture elongation of 11%. This study clearly demonstrates that [OSSO

]

‍-type hafnium complexes are rare non-metallocene catalysts for the isotactic polymerization of 4M1P

and also provide access to the enhancement of PMP molecular weight by suppressing chain transfer to aluminum.

关键词

Keywords

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吡啶胺基铪催化4-甲基-1-戊烯与1-己烯聚合研究